Article
Chemistry, Multidisciplinary
Emi Ito, Shinjiro Takano, Toshikazu Nakamura, Tatsuya Tsukuda
Summary: Targeted syntheses of MM ' Au-36(PET)(24) were achieved through hydride-mediated fusion reactions, resulting in bi-icosahedral MM ' Au-21 cores composed of M@Au-12 and M '@Au-12 superatoms. Counterintuitive results were explained by a bent bonding model based on tilted bonding interaction between the superatomic orbitals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Wen-Di Liu, Jia-Qi Wang, Shang-Fu Yuan, Xi Chen, Quan-Ming Wang
Summary: Silver nanoclusters protected by amino acids were synthesized and characterized in this study. Chiral superatomic silver nanoclusters with T symmetry were prepared, showing homochirality as evidenced by CD measurements. The CD signals were mainly contributed by the Ag s,p states near the Fermi level.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Haru Hirai, Shinjiro Takano, Takuya Nakashima, Takeshi Iwasa, Tetsuya Taketsugu, Tatsuya Tsukuda
Summary: In this study, a series of MAu12(dppe)(5)Cl-2 compounds with icosahedral structures were synthesized and their electronic structures, photoluminescence, and photocatalytic properties were systematically investigated. Doping an M element at the lower left of the periodic table expanded the energy gap between HOMO and LUMO, resulting in enhanced photoluminescence quantum yield. MAu12 (M=Pt, Rh, or Ir) exhibited higher photocatalytic activity than Au-13.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Ngo Thi Lan, Nguyen Thi Mai, Duong Duc La, Nguyen Minh Tam, Son Tung Ngo, Ngo Tuan Cuong, Nguyen Van Dang, Thu Thi Phung, Nguyen Thanh Tung
Summary: By doping the Au-10(2+) cluster with 3d transition metal atoms, the study explores superatomic clusters as analogues of more complex molecules. It is found that Au9M2+ exhibits different structural evolution patterns and stable magnetic behavior.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Xiaoshuang Ma, Lin Xiong, Lubing Qin, Yun Tang, Guanyu Ma, Yong Pei, Zhenghua Tang
Summary: In this study, the first homoleptic alkynyl-protected AgCu superatomic nanocluster was reported, along with a similar structure bimetallic nanocluster. Despite the similar Ag-8 cube structure, subtle differences exist between the two clusters, resulting in significantly different optical absorbance features.
Article
Chemistry, Physical
Shao-Yu Kang, Zi-Ang Nan, Quan-Ming Wang
Summary: The superatomic orbital splitting (SOS) method is developed to understand the electronic structures of coinage metal nanoclusters by taking the shape of the metal core into account. By treating nanoclusters as superatoms, the electron configuration of nonmagic-number nanoclusters can be qualitatively analyzed without complex calculations, which is crucial for understanding the stability of the clusters.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Tao Jia, Zong-Jie Guan, Chengkai Zhang, Xiao-Zhao Zhu, Yun-Xin Chen, Qian Zhang, Yang Yang, Di Sun
Summary: A novel eight-electron superatomic copper nanocluster Cu31 is presented, which features an inherent chiral metal core and shows absorption and emission characteristics in the near-infrared (NIR) region. The study also reveals the significance of close contacts between neighboring clusters for the cluster formation and crystallization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Shiv N. Khanna, Arthur C. Reber, Dinesh Bista, Turbasu Sengupta, Ryan Lambert
Summary: Cluster science is gaining attention due to the size and composition-dependent properties of clusters. The superatom concept provides a unifying framework for understanding cluster behaviors. Ligated metal-chalcogenide clusters exhibit periodic electronic structures and predictable redox properties.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Yu-Rong Ni, Michael N. Pillay, Tzu-Hao Chiu, Ying-Yann Wu, Samia Kahlal, Jean-Yves Saillard, C. W. Liu
Summary: The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19(dtp)(12)] and [PdHAg20(dtp)(12)](+) are reported. Addition of a single Ag atom to [PdHAg19(dtp)(12)] through the reaction of trifluoroacetic acid yields [PdHAg20(dtp)(12)](+) in 55% yield. Further modification of the shell results in the formation of [PdAg21(dtp)(12)](+) via an internal redox reaction. The interstitial hydride in [PdHAg19(dtp)(12)] and [PdHAg20(dtp)(12)](+) contributes its 1s(1) electron and occupies a PdAg3 tetrahedron.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Chen Yan, Jiuqi Yi, Peng Wang, Dan Li, Longjiu Cheng
Summary: Researchers have designed new structures of gold nanoclusters using the Au-4 unit, showing high stability and following the superatom network model. They also predicted 2D monolayer and 3D crystal structures of Au-4 based on these clusters, demonstrating metallic properties.
Article
Nanoscience & Nanotechnology
Qing Tang, Fuhua Li, De-en Jiang
Summary: The study uses density functional theory to calculate the crystal structure of a representative superatomic gold cluster under various pressures, revealing the formation of covalent bonds between clusters with increasing compression, leading to structural changes and transitions in physical properties.
ACS NANOSCIENCE AU
(2021)
Article
Chemistry, Multidisciplinary
Gowri Udayangani Kuda-Singappulige, Phillip S. Window, Christopher A. Hosier, Ian D. Anderson, Christine M. Aikens, Christopher J. Ackerson
Summary: The crystal structures of four ligand-rotational isomers of Au-25(PET)(18) are presented. Two new isomers are discovered, and two higher-quality structures of previously solved clusters are also provided. The chiral structure of Au-25(SR)(18) is the first of its kind. The analysis of the structures sheds light on the empirical ligand conformation landscape for Au-25(SR)(18) clusters, showing restricted and interdependent dihedral angles within the PET ligand. The influence of ligand conformational isomerism on optical and electronic properties is also investigated.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Sakiat Hossain, Sayuri Miyajima, Takeshi Iwasa, Ryo Kaneko, Taishu Sekine, Ayaka Ikeda, Tokuhisa Kawawaki, Tetsuya Taketsugu, Yuichi Negishi
Summary: Icosahedral noble-metal 13-atom nanoclusters can form connected structures by vertex sharing, creating superatomic molecules. A new superatomic molecule, [Ag23Pd2(PPh3)(10)Cl-7], was synthesized and shown to be stable with strong superatomic frameworks. Experimental and theoretical analyses suggested that it is more stable than [Ag-25(PPh3)(10)Cl-7].
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Li Tang, Shiyao Deng, Shuxin Wang, Yong Pei, Manzhou Zhu
Summary: A thiolated-alloy nanocluster (AuCu)32 with a unique hollow core structure composed of Au14Cu6 has been synthesized. The cluster has been confirmed by various analytical methods, and the presence of six 2e alloy superatomic Au3Cu2+ units has been further supported by electronic structure analysis. The stable electronic structure of the nanocluster may have potential applications in catalysis.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Puru Jena
Summary: Superatoms are tailored atomic clusters that mimic the chemistry of atoms in the periodic table. They have unique properties due to their large size and non-spherical geometry, which enable unusual reactions and the formation of cluster assembled materials. This perspective focuses on superhalogens and their ability to form stable chemical bonds and exhibit unconventional oxidation states, highlighting their potential applications in various fields including solar cells and solid-state batteries.
JOURNAL OF THE INDIAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Chun-Fu Chang, Hikaru Kuramochi, Manish Singh, Rei Abe-Yoshizumi, Tatsuya Tsukuda, Hideki Kandori, Tahei Tahara
Summary: The varied excited-state relaxation dynamics in different microbial rhodopsins mainly originate from the difference in ground-state heterogeneity, specifically the protonation/deprotonation of the PRSB counterion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Renee W. Y. Man, Hong Yi, Sami Malola, Shinjiro Takano, Tatsuya Tsukuda, Hannu Hakkinen, Masakazu Nambo, Cathleen M. Crudden
Summary: This study reports the first chiral Au-10 nanoclusters stabilized by chiral bis N-heterocyclic carbene (bisNHC) ligands and confirms their structure and properties. DFT calculations further reveal the electronic structure and optical characteristics, as well as chirality transfer, of this nanocluster.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Biochemistry & Molecular Biology
Lewei Wang, Tsubasa Omoda, Kiichirou Koyasu, Tatsuya Tsukuda
Summary: In this study, we successfully demonstrated the atomically precise synthesis of gold cluster cations by magnetron sputtering onto a PEG solution of dppp. The formation of cationic species was confirmed through UV-vis absorption spectroscopy and electrospray ionization mass spectrometry, and the involvement of [Au(dppp)(2)](+) cations as key components in cluster formation was proposed based on experimental observations.
Article
Chemistry, Physical
Shun Ito, Yuriko Tasaka, Katsunosuke Nakamura, Yuki Fujiwara, Keisuke Hirata, Kiichirou Koyasu, Tatsuya Tsukuda
Summary: The electron binding energies of gold/silver-based clusters with M13 superatomic cores were reexamined using gas-phase photoelectron spectroscopy. The previous results were found to be contaminated by signals from two-photon electron detachment, but the effects of doping and ligation on electron binding energies were not significantly affected.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Physics, Applied
Masaomi Sanekata, Yuki Nakagomi, Mutsuki Hirayama, Hiroshi Nishida, Nobuo Nishimiya, Masahide Tona, Hiroaki Yamamoto, Keizo Tsukamoto, Kiyokazu Fuke, Keijiro Ohshimo, Kiichirou Koyasu, Fuminori Misaizu
Summary: The study used reflexron-type time-of-flight mass spectrometry to analyze deep oscillation magnetron sputtering (DOMS) and revealed the plasma build-up process from non-metallic plasma to metallic plasma, as well as the rarefaction and refilling processes of Ar.
JOURNAL OF APPLIED PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Megumi Suyama, Shinjiro Takano, Tatsuya Tsukuda
Summary: In this study, we investigated the effects of ligands on spontaneous electron transfer between alkanethiolate-protected metal clusters in solution. The rate of electron transfer showed a turnover behavior depending on the total chain length of the ligands. The promotion of electron transfer by longer alkanethiolates was attributed to the elongation of lifetime and the contraction of distance between the clusters due to stronger van der Waals interaction. This alkyl-chain-promoted electron transfer is specific to ultrasmall clusters in solution due to nonuniform ligand layer formation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Katsunosuke Nakamura, Shun Ito, Kiichirou Koyasu, Tatsuya Tsukuda
Summary: The electronic structures of chemically synthesized silver-based clusters with icosahedral X@Ag-12 core were studied using gas-phase photoelectron spectroscopy and density functional theory calculations. The HOMO binding energy and LUMO energy relative to the vacuum level were determined for X = Ag or Au. The destabilization of HOMO in [XAg16(TBBT)(12)](3-) compared to [XAg24(DMBT)(18)](-) was attributed to the larger negative charge from the ligand layers.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Haru Hirai, Takuya Nakashima, Shinjiro Takano, Yukatsu Shichibu, Katsuaki Konishi, Tsuyoshi Kawai, Tatsuya Tsukuda
Summary: In this study, the effects of single-atom doping on the chiroptical properties of gold superatoms were investigated. It was found that single-atom doping can improve the chiroptical properties of gold superatoms, and this study provides a rational guide for enhancing their chiroptical activity.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Biochemical Research Methods
Katarzyna Joanna Malawska, Shinjiro Takano, Kounosuke Oisaki, Haruaki Yanagisawa, Masahide Kikkawa, Tatsuya Tsukuda, Motomu Kanai
Summary: We developed a method for bioconjugation of Au25 nanoclusters to monoclonal antibodies. This method allows for the attachment of the nanoclusters to rarely exposed tryptophan residues, making them suitable for high-resolution imaging techniques such as cryo-EM and cryo-ET. The use of hydroxylamine reagents instead of N-oxyl radicals improved the selectivity of the bioconjugation process, enabling the labeling of acid-sensitive proteins.
BIOCONJUGATE CHEMISTRY
(2023)
Article
Chemistry, Physical
Shinjiro Takano, Emi Ito, Toshikazu Nakamura, Tatsuya Tsukuda
Summary: Heterometal doping is an effective method to modulate the electronic structure of chemically modified gold clusters. We successfully synthesized Ni-doped gold clusters and compared them with Pd- and Pt-doped clusters, finding that the Ni-doped clusters have a slightly contracted core. The contraction of the Ni@Au12 core leads to a period-dependent doping effect, which cannot be solely explained by the modified jellium model. This work provides guidance for designing gold clusters with heterometal doping within a specific group of the periodic table.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Kosuke Sakamoto, Shinya Masuda, Shinjiro Takano, Tatsuya Tsukuda
Summary: Partially thiolated atomically precise Au cluster catalysts were developed by controlled calcination of presynthesized thiolate-protected Au clusters on a porous carbon support. The partially thiolated Au25 cluster catalysts exhibited comparable catalytic activity to that of the thiolate-free Au25 cluster for benzyl alcohol oxidation, but higher durability. These catalysts are promising model catalysts with both high activity and durability.
Article
Chemistry, Physical
Kosuke Sakamoto, Shinya Masuda, Shinjiro Takano, Tatsuya Tsukuda
Summary: Partially thiolated atomically precise Au cluster catalysts were obtained by controlled calcination of presynthesized thiolate-protected Au clusters on a porous carbon support. The partially thiolated Au25 cluster catalysts showed comparable catalytic activity to the thiolate-free Au25 cluster catalysts for benzyl alcohol oxidation, while exhibiting higher durability. This work demonstrates that partially ligated, atomically precise metal clusters anchored by noncovalent ligand-support interaction are promising model catalysts with both high activity and durability.
Article
Chemistry, Multidisciplinary
Emi Ito, Shun Ito, Shinjiro Takano, Toshikazu Nakamura, Tatsuya Tsukuda
Summary: The validity of the supervalence bond model in the Au23 core was verified through experimental validation, and [M1Au37(PET)24]- (M = Pd and Pt) with the same electronic and structure as Au38(PET)24 were successfully synthesized. Anion photoelectron spectroscopy confirmed the predictions of the supervalence bond model.
Article
Chemistry, Multidisciplinary
Paul A. Lummis, Kimberly M. Osten, Tetyana Levchenko, Maryam Sabooni Asre Hazer, Sami Malola, Bryan Owens-Baird, Alex J. Veinot, Emily L. Albright, Gabriele Schatte, Shinjiro Takano, Kirill Kovnir, Kevin G. Stamplecoskie, Tatsuya Tsukuda, Hannu Hakkinen, Masakazu Nambo, Cathleen M. Crudden
Summary: The synthesis of a toroidal Au-10 cluster stabilized by N-heterocyclic carbene and halide ligands is described via reduction of NHC-Au-X complexes (X = Cl, Br, I). The halide ligands significantly affect the formation, stability, and conversions of these clusters. The bromide derivative readily converts to a biicosahedral Au-25 cluster at room temperature, while the iodide derivative shows significant formation of Au-25 upon reduction of NHC-Au-I. The isolated bromide derivative of Au-25 cluster exhibits relatively high photoluminescence quantum yield due to the high rigidity enforced by multiple CH-pi interactions.
Article
Chemistry, Multidisciplinary
Taro Shigeta, Shinjiro Takano, Tatsuya Tsukuda
Summary: The structure of the new sulfur-containing gold cluster Au18S2(STipb)(12) was revealed through single-crystal X-ray diffraction analysis, showing a deformed octahedral Au-6 core clutched by two tridentate S[Au-2(STipb)(2)](3) units in an interlocked manner.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)